Process for producing polyester-polycarbonate type thermoplastic polyester elastomer and polyester-polycarbonate type thermoplastic polyester elastomer

ABSTRACT

The present invention is a process for producing a polyester-polycarbonate type thermoplastic polyester elastomer in which a hard segment consisting of a polyester constructed of aromatic dicarboxylic acid, and an aliphatic or alicyclic diol, and a soft segment consisting mainly of aliphatic polycarbonate are connected, comprising at least a step of increasing the molecular weight of an aliphatic polycarbonate diol by a reaction of an aliphatic polycarbonate diol and a chain extender, and a step of reacting aliphatic polycarbonate and a polyester constructed of aromatic dicarboxylic acid and an aliphatic or alicyclic diol in the molten state.

TECHNICAL FIELD

The present invention relates to a process for producing apolyester-polycarbonate type thermoplastic polyester elastomer, and apolyester-polycarbonate type thermoplastic polyester elastomer. Moreparticularly, the present invention relates to a process for producing apolyester-polycarbonate type thermoplastic polyester elastomer excellentin heat resistance, light resistance, heat aging resistance, waterresistance, and low temperature property, particularly apolyester-polycarbonate type thermoplastic polyester elastomer which canbe used in various molding materials including fibers, films, andsheets, further particularly, a polyester-polycarbonate typethermoplastic polyester elastomer which is suitable for elastic yarnsand molding materials such as boots, gears, tubes and packings, and isuseful in utility requiring heat aging resistance, water resistance, lowtemperature property and heat resistance such as automobiles, andhousehold appliances, for example, joint boots, and electric wirecovering materials, and a polyester-polycarbonate type thermoplasticpolyester elastomer obtained by the process.

BACKGROUND ART

As the thermoplastic polyester elastomer, thermoplastic polyesterelastomers in which a soft segment is a crystallizable polyesterincluding polybutylene terephthalate (PBT), and polybutylene naphthalate(PBN), and a hard segment is polyoxyalkylenes such as polytetramethyleneglycol (PTNG) and/or a polyester such as polycaprolactone (PCL), andpolybutylene adipate (PBA), have previously been known, and put intopractice (e.g. Patent Publications 1, 2).

-   Patent Publication 1: JP-A No. 10-17657-   Patent Publication 2: JP-A No. 2003-192778

However, it is known that a polyester polyether-type elastomer usingpolyoxyalkylenes in the soft segment is excellent in water resistanceand low temperature property, but is inferior in heat aging resistance,and a polyester-polyester type elastomer using a polyester in the softsegment is excellent in heat aging resistance, but is inferior in waterresistance and low temperature property.

For the purpose of solving the aforementioned defects,polyester-polycarbonate type elastomers using polycarbonate in the softsegment have been proposed (see e.g. Patent Publications 3 to 8.

-   Patent Publication 3: JP-B No. 7-39480-   Patent Publication 4: JP-A No. 5-295094-   Patent Publication 5: JP-A No. 10-231415-   Patent Publication 6: JP-A No. 10-182782-   Patent Publication 7: JP-A No. 2001-206939-   Patent Publication 8: JP-A No. 2001-240663

The aforementioned problems are solved, but the polyesterpolycarbonate-type thermoplastic polyester elastomers disclosed in thesePatent Publications have a problem that the resultingpolyester-polycarbonate type thermoplastic polyester elastomer isinferior in retainability of blocking property when thepolyester-polycarbonate type elastomer is retained in the molten state(hereinafter, also simply referred to as blocking property retainabilityin some cases), for the reason of the small molecular weight ofpolycarbonate diol used as a raw material.

For example, since low blocking property leads to a problem that themelting point of the polyester-polycarbonate type thermoplasticpolyester elastomer is lowered, for example, in the case of the jointboots and electric wire covering materials, deficiency of heatresistance becomes a problem in some cases in utility of use under thehigh temperature environment such as a periphery of an engine ofautomobiles, in some cases. Patent Publications 4, 7 and 8 disclose risein the melting point is realized by introducing a naphthalate skeletonas a polyester component, but since introduction of the naphthalateskeleton is expensive, rise in the melting point realized by a polyestercomponent having an inexpensive terephthalate skeleton is desired. Inaddition, regarding a polyester-polycarbonate type thermoplasticpolyester elastomer consisting of a polyester component having anaphthalate skeleton, rise in the melting point corresponding toincrease in the cost is demanded.

In addition, in recent years, from a view point of the environmentalload and the cost reduction, reutilization of off-specificationproducts, or recycle of commercial goods is demanded. In order tosatisfy the demand, high blocking property retainability is required.From the background, development of a polyester-polycarbonate typethermoplastic polyester elastomer having high blocking property andexcellent retainability of the blocking property is strongly solicited.

On the other hand, Patent Publications 7 and 8 disclose a process ofreacting a polyester component forming a hard segment and apolycarbonate diol component forming a soft segment in the molten stateto form a block polymer, and increasing the molecular weight with achain extender. The process is an effective method as a method ofincreasing the molecular weight of a block polymer, but since theblocking property and retainability of the blocking property undergogreatly control mainly by a reaction during formation of the blockpolymer, it is difficult to improve the blocking property and theblocking property retainability by a method of increasing the molecularweight with a chain extender after formation of the block polymer.Therefore, in the prior art, a polyester-polycarbonate typethermoplastic polyester elastomer having preferable property has notbeen obtained. For this reason, establishment of a process foreconomically producing a polyester-polycarbonate type thermoplasticpolyester elastomer having preferable property is strongly solicited.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention

In view of the previous problems possessed by thepolyester-polycarbonate type thermoplastic polyester elastomer, anobject of the present invention is to provide an economic process forproducing a polyester-polycarbonate type thermoplastic polyesterelastomer having excellent heat resistance, heat aging resistance, waterresistance, light resistance and low temperature property, and excellentin blocking property retainability, and a polyester-polycarbonate typethermoplastic polyester elastomer obtained by it.

Means to Solve the Problems

The present invention for attaining the object is as follows:

-   [1] A process for producing a polyester-polycarbonate type    thermoplastic polyester elastomer in which a hard segment consisting    of a polyester constructed of aromatic dicarboxylic acid and an    aliphatic or alicyclic diol, and a soft segment consisting mainly of    aliphatic polycarbonate are connected, comprising at least the    following steps:-   step 1: a step of obtaining the aliphatic polycarbonate having the    increased molecular weight by a reaction of an aliphatic    polycarbonate diol and a chain extender,-   step 2: a step of reacting the aliphatic polycarbonate and the    polyester in the molten state.

Hereinafter, different terms are used in principle such thatpolycarbonate in which the molecular weight has not been increasedbefore the reaction with the chain extender in the step 1 is referred toas aliphatic polycarbonate diol, and polycarbonate in which themolecular weight has been increased after the reaction is referred asaliphatic polycarbonate.

-   [2] The process for producing a polyester-polycarbonate type    thermoplastic polyester elastomer according to [1], wherein the step    1 and the step 2 are performed in different reaction tanks.-   [3] The process for producing a polyester-polycarbonate type    thermoplastic polyester elastomer according to [1] or [2], wherein    the number average molecular weight of the aliphatic polycarbonate    is 5000 to 80000.-   [4] A polyester-polycarbonate type thermoplastic polyester elastomer    obtained by the process as defined in any one of [1] to [3],    characterized in that when a cycle of raising the temperature of the    polyester-polycarbonate type thermoplastic polyester elastomer from    room temperature to 300° C. at the temperature raising rate of 20°    C./min using a differential scanning calorimeter, retaining the    temperature at 300° C. for 3 minutes, and lowering the temperature    to room temperature at the temperature lowering rate of 100° C./min    is repeated three times, the melting point difference (Tm1−Tm3)    between the melting point (Tm1) obtained by first measurement and    the melting point (Tm3) obtained by third measurement is 0 to 50° C.-   [5] The polyester-polycarbonate type thermoplastic polyester    elastomer according to [4], wherein the hard segment consists of a    polybutylene terephthalate unit, and the melting point of the    resulting polyester-polycarbonate type thermoplastic polyester    elastomer is 200 to 225° C.-   [6] The polyester-polycarbonate type thermoplastic polyester    elastomer according to [4], wherein the hard segment consists of a    polybutylene naphthalate unit, and the melting point of the    resulting polyester-polycarbonate type thermoplastic polyester    elastomer is 215 to 240° C.-   [7] The polyester-polycarbonate type thermoplastic polyester    elastomer according to any one of [4] to [6], wherein letting the    average chain length of the hard segment calculated using nuclear    magnetic resonance (NMR method) to be x, and letting the average    chain length of the soft segment to be y, the average chain    length (x) of the hard segment is 5 to 20, and blocking property (B)    calculated by the following (1) equation is 0.11 to 0.45.    B=1/x+1/y  (1)

EFFECT OF THE INVENTION

The process for producing a polyester-polycarbonate type thermoplasticpolyester elastomer of the present invention has an advantage that, byintroducing a step of increasing the molecular weight of an aliphaticpolycarbonate diol by a reaction of an aliphatic polycarbonate diol anda chain extender (step 1: hereinafter, referred to as raw materialmolecular weight up step in some cases) prior to the previously knownstep of reacting an aliphatic polycarbonate diol and an aromaticpolyester (hereinafter, a polyester constructed of aromatic dicarboxylicacid and an aliphatic or alicyclic diol is referred to as aromaticpolyester in some cases) in the molten state (step 2: hereinafter,referred to as blocking reaction step in some cases), a high qualitypolyester-polycarbonate type thermoplastic polyester elastomer havingthe following properties can be produced economically and stably by asimple method of increasing the molecular weight of aliphaticpolycarbonate supplied to a blocking reaction. In addition, the processis preferably such that the step 1 and the step 2 are performed indifferent reaction tanks, and has an advantage that the elastomer can beproduced utilizing a general-use apparatus for producing a polyesterusing such the form that a transesterification or esterificationreaction and a polycondensation reaction are performed in separatereaction tanks.

In addition, the polyester-polycarbonate type thermoplastic polyesterelastomer of the present invention obtained by the process is improvedin blocking property and blocking property retainability whilemaintaining characteristics of the polyester-polycarbonate typethermoplastic elastomer being good in heat resistance, and excellent inheat aging property, water resistance and low temperature property. Dueto high blocking property, reduction in heat resistance resulting fromreduction in the melting point is suppressed, and a mechanical naturesuch as a hardness, a tensile strength, and an elastic modulus isimproved. In addition, by improvement in blocking propertyretainability, since variation of blocking property at moldingprocessing is suppressed, uniformity of quality of molded articles canbe enhanced. In addition, due to the characteristics, since recycleproperty is enhanced, this can lead to reduction in environmental loadand cost. Therefore, like this, since the polyester-polycarbonate typethermoplastic polyester elastomer of the present invention has theexcellent properties and advantages, it can be used in various moldingmaterials including fibers, films, and sheets. In addition, theelastomer is also suitable in elastic yarns, and molding materials suchas boots, gears, tubes, and packings and, for example, is useful inutility requiring heat aging resistance, water resistance, and lowtemperature property such as automobiles, and household parts,specifically, utility such as joint boots, and electric wire coveringmaterials. Particularly, the elastomer can be suitably used as materialsfor parts requiring high heat resistance, such as joint boots used in aperiphery of an engine of automobiles, and electric wire coveringmaterials.

BEST MODE FOR CARRYING OUT THE INVENTION

The polyester-polycarbonate type thermoplastic polyester elastomer ofthe present invention will be explained in detail below.

In the polyester-polycarbonate type thermoplastic polyester elastomer ofthe present invention, as aromatic dicarboxylic acid constituting apolyester of the hard segment, normal aromatic dicarboxylic acid iswidely used without any limitation. It is desirable that main aromaticdicarboxylic acid is terephthalic acid or naphthalene dicarboxylic acid.Examples of other acid component include aromatic dicarboxylic acidssuch as diphenyldicarboxylic acid, isophthalic acid, and sodium5-sulfoisophthalate, alicyclic dicarboxylic acids such ascyclohexanedicarboxylic acid, and anhydrous tetrahydrophthalic acid, andaliphatic dicarboxylic acids such as succinic acid, glutaric acid,adipic acid, azelaic acid, sebacic acid, dodecanedionic acid, dimeracid, and hydrogenated dimer acid. These are used in such the range thatthe melting point of resins is not greatly lowered, and the amountthereof is less than 30 mol %, preferably less than 20 mol % of a totalacid component.

In addition, in the polyester-polycarbonate type thermoplastic polyesterelastomer of the present invention, as aliphatic or alicyclic diolconstituting a polyester of the hard segment, general aliphatic oralicyclic diols are widely used without any limitation. It is desirablethat the diol is mainly alkylene glycols of the carbon number of 2 to 8.Specifically, examples include ethylene glycol, 1,3-propylene glycol,1,4-butanediol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol.1,4-butanediol and 1,4-cyclohexanedimethanol are most preferable.

As a component constituting a polyester of the hard segment, a componentconsisting of a butylene terephthalate unit or a butylene naphthalateunit is preferable from a view point of physical properties, moldingproperty and the cost. In the case of the naphthalate unit, a 2,6 bodyis preferable.

An aromatic polyester suitable as a polyester constituting the hardsegment in the polyester-polycarbonate type thermoplastic polyesterelastomer of the present invention can be easily obtained according tothe conventional process of producing a polyester. It is desirable thatsuch the polyester has generally the number average molecular weight of10000 to 40000.

The aliphatic polycarbonate chain constituting the soft segment in thepolyester-polycarbonate type thermoplastic polyester elastomer of thepresent invention preferably consists mainly of an aliphatic diolresidue of the carbon number of 2 to 12. Examples of the aliphatic diolinclude ethylene glycol, 1,3-propylene glycol, 1,4-butanediol,1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol,2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol,2,4-diethyl-1,5-pentanediol, 1,9-nonanediol, and2-methyl-1,8-octanediol. Particularly, from a point of flexibility andlow temperature property of the resulting polyester-polycarbonate typethermoplastic polyester elastomer, an aliphatic diol of the carbonnumber of 5 to 12 is preferable. These components may be used alone, ortwo or more kinds may be used together, if necessary, based on instancesexplained below.

As the aliphatic polycarbonate diol having good low temperatureproperty, constituting the soft segment of the polyester-polycarbonatetype thermoplastic polyester elastomer in the present invention, a diolhaving the low melting point (e.g. 70° C. or lower), and the low glasstransition temperature is preferable. Generally, since an aliphaticpolycarbonate diol consisting of 1,6-hexanediol used in forming the softsegment of the polyester-polycarbonate type thermoplastic polyesterelastomer has the low glass transition temperature of around −60° C.,and the melting point of around 50° C., low temperature property becomesgood. Besides, since an aliphatic polycarbonate diol obtained bycopolymerizing the aliphatic polycarbonate diol with, for example, thesuitable amount of 3-methyl-1,5-pentanediol has the slightly higherglass transition point than that of the original aliphatic polycarbonatediol, but has the lowered melting point or becomes amorphous, thiscorresponds to the aliphatic polycarbonate diol having good lowtemperature property. In addition, for example, since the aliphaticpolycarbonate diol consisting of 1,9-nonane diol and2-methyl-1,8-octanediol has the sufficiently low melting point of around30° C., and the sufficiently low glass transition temperature of around−70° C., this corresponds to the aliphatic polycarbonate diol havinggood low temperature property.

The aliphatic polycarbonate diol is not necessarily composed of only apolycarbonate component, and may be copolymerized with the small amountof other glycol, dicarboxylic acid, an ester compound or an ethercompound. Examples of the copolymerization component include glycolssuch as a dimer diol, a hydrogenated dimer diol and a modified diolthereof, dicarboxylic acids such as dimer acid, and hydrogenated dimeracid, poly- or oligoesters consisting of aliphatic, aromatic oralicyclic dicarboxylic acids and glycols, polyesters or oligoestersconsisting of ε-caprolactone, and alkylene glycols or oligoalkyleneglycols such as polytetramethylene glycol, and polyoxyethylene glycol.

The copolymerization component can be used at such the extent that theeffect of the aliphatic polycarbonate segment does not substantiallydisappear. Specifically, the amount of the copolymerization component is40 parts by weight or less, preferably 30 parts by mass or less, morepreferably 20 parts by mass or less based on 100 parts by mass of thealiphatic polycarbonate segment. When the copolymerization amount is toogreat, the resulting polyester-polycarbonate type thermoplasticpolyester elastomer becomes inferior in heat aging resistance, and waterresistance.

As the soft segment, a copolymerization component such as polyalkyleneglycol such as polyethylene glycol, and polyoxytetramethylene glycol orpolyester such as polycaprolactone, and polybutylene adipate may beintroduced into the polyester-polycarbonate type thermoplastic polyesterelastomer of the present invention, as far as the effect of theinvention is not lost. The content of the copolymerization component isusually 40 parts by mass or less, preferably 30 parts by mass or less,more preferably 20 parts by mass or less based on 100 parts by mass ofthe soft segment.

In the polyester-polycarbonate type thermoplastic polyester elastomer ofthe present invention, the mass part ratio of the polyester constitutingthe hard segment, and the aliphatic polycarbonate and the copolymercomponent constituting the soft segment is generally in the range ofhard segment:soft segment=30:70 to 95:5, preferably 40:60 to 90:10, morepreferably 45:55 to 87:13, most preferably 50:50 to 85:15.

In the present invention, it is necessary that the process for producingthe polyester-polycarbonate type thermoplastic polyester elastomerhaving the aforementioned composition comprises at least the followingsteps.

-   Step 1: a step of obtaining aliphatic polycarbonate having the    increased molecular weight by a reaction of an aliphatic    polycarbonate diol and a chain extender,-   Step 2: a step of reacting the aliphatic polycarbonate and a    polyester in the molten state.

In the prior art disclosed in Patent Publications 4, 7 and 8, theelastomer was produced by only the step 2 of reacting the aliphaticpolycarbonate diol and the aromatic polyester in the molten state, thatis, a step similar to a blocking reaction step, but in the presentinvention, it is the great characteristic that, prior to the blockingreaction step, a raw material molecular weight up step of increasing themolecular weight of the aliphatic polycarbonate diol by a reaction ofthe aliphatic polycarbonate diol and the chain extender is introduced,and the blocking reaction is performed using the aliphatic polycarbonatehaving the increased molecular weight obtained by the step. By thestrategy, it has become possible to economically and stably produce ahigh quality polyester-polycarbonate type thermoplastic polyesterelastomer described later, having improved properties possessed by thepolyester-polycarbonate type thermoplastic polyester elastomer obtainedby the prior art.

In the present invention, the molecular weight of the aliphaticpolycarbonate having the increased molecular weight is preferably 5000to 80000 in terms of the number average molecular weight. As themolecular weight is greater, blocking property and blocking propertyretainability are improved. On the other hand, conversely, when themolecular weight is too high, compatibility of the hard segment and thesoft segment is reduced, being not preferable. Therefore, the molecularweight of the polycarbonate diol is preferably 5000 to 80000, morepreferably 7000 to 70000, further preferably 8000 to 60000 in terms ofthe number average molecular weight. When the molecular weight of thepolycarbonate diol is less than 5000, blocking property and blockingproperty retainability are deteriorated, being not preferable.Conversely, when the molecular weight of the polycarbonate diol exceeds80000, compatibility of the hard segment and the soft segment isreduced, mechanical property such as a strength and an elongation of theresulting polyester-polycarbonate type thermoplastic polyester elastomeris inferior, and fluctuation of the properties becomes great, being notpreferable.

For example, the molecular weight of a commercially available aliphaticpolycarbonate diol is 3000 or less. Therefore, it is a preferableembodiment that the aliphatic polycarbonate diol in the preferable rangeis obtained using the commercially available aliphatic polycarbonatediol of the low molecular weight.

The chain extender is not limited as far as it is a polyfunctionalactive compound containing 2 or more functional groups having reactivitywith a terminal hydroxyl group of the aliphatic polycarbonate diol inone molecule. The number of functional groups is not limited as far asit is 2 or more, and a difunctional group is preferable. Examplesinclude diphenyl carbonate, diisocyanate, and dicarboxylic anhydride. Ifthe small amount, a polyfunctional, i.e., tri- or more-functionalcompound may be used. In place of diphenyl carbonate, a carbonatecompound such as dimethyl carbonate, diethyl carbonate, dipropylcarbonate, diisopropyl carbonate, dibutyl carbonate, and dimethylcarbonate may be used. Alternatively, it may be cyclic carbonate such asethylene carbonate, or a dithio carbonate compound. Alternatively, inplace of a phenoxy group of a diphenyl carbonate, a carbonyl compoundhaving a nitrogen-containing compound residue such as imidazole andlactam may be used.

As the low-molecular aliphatic polycarbonate diol before increase in themolecular weight by the aforementioned method, it is preferable toutilize a commercially available diol, without any limitation. Forexample, when a special copolymer is required as the aliphaticpolycarbonate diol, a diol which was especially prepared may be used.

In the aforementioned method, adjustment of the molecular weight of theresulting aliphatic polycarbonate can be performed by changing themolecular weight of the aliphatic polycarbonate diol which is a startingraw material, or the charging ratio of the aliphatic polycarbonate dioland the chain extender. Alternatively, the molecular weight may be alsoadjusted by the reaction time. As the molecular weight of a starting rawmaterial is higher, or the charging ratio of the chain extender issmaller, the molecular weight of the resulting aliphatic polycarbonatebecomes higher. The molecular weight may be conveniently set dependingon the goal molecular weight.

As a reaction method conducted by the aforementioned method, reactioncondition such as the reaction temperature, the reaction time, stirringcondition and the like is not limited, as far as the aliphaticpolycarbonate diol having the lower molecular weight than the finalmolecular weight and the chain extender are mixed and reacted in areactor. For example, when diphenyl carbonate is used as the chainextender, the reaction is preferably performed by the following method.

For example, a polycarbonate diol (molecular weight 2000) consisting ofcommercially available 1,6-hexanediol and diphenyl carbonate are chargedunder the normal pressure to under pressure, the mixture is heated, andthe reaction can proceed in the molten state while removing phenolproduced by the reaction. A method of removing phenol is not limited.Examples include a method of reducing the pressure with a vacuum pump oran ejector, and a method of flowing an inert gas.

The charging mole ratio of the polycarbonate diol and the diphenylcarbonate in the reaction [diphenyl carbonate/polycarbonate diol(molecular weight 2000) consisting of 1,6-hexanediol] is preferably inthe range of 0.5 to 1.5, more preferably in the range of 0.6 to 1.4.When the ratio is outside this range, it is difficult to maintain thedesired molecular weight. And, at charging of the raw materials or atthe reaction, it is preferable that the interior of a reaction can isreplaced with an inert gas to remove oxygen. When the amount ofremaining oxygen is greater, the reaction product may be colored, beingnot preferable. The temperature in the reaction can at charging of theraw materials is preferably 100 to 130° C. After charging of rawmaterials, the temperature is raised to 150 to 250° C. while stirring,to proceed the reaction. The reaction temperature is preferably 170 to240° C., further preferably 180 to 230° C. Then the temperature is lowerthan 150° C., the reaction rate is very slow, the molecular weight doesnot reach a desired one, and the reaction time becomes very long,resulting in the high production cost. Conversely, when the temperatureis higher than 250° C., a degradation reaction due to thermaldegradation is increased, and coloration of the reaction product isseen, being not preferable. When the temperature reaches thepredetermined reaction temperature, the pressure in the reaction can isgradually reduced from the normal pressure to 530 Pa or lower over 30 to120 minutes, thereafter, phenol eliminated by the reaction is preferablyremoved. The pressure is more preferably 400 Pa or lower, furtherpreferably, 270 Pa or lower. When the pressure is higher than 530 Pa,the rate of removing phenol eliminated by progression of the reactionbecomes very slow, the molecular weight does not reach a desired one,and the reaction time becomes very long, resulting in the highproduction cost. The time required for a reaction after attainment ofthe predetermined vacuum degree is preferably shorter. The time ispreferably 240 minutes or shorter, more preferably 180 minutes orshorter, further preferably 120 minutes or shorter. It is preferablethat the molecular weight of polycarbonate diol is controlled using astirring power of the reaction can as the measure.

In the present invention, the reaction condition of the blockingreaction step of the step 2 is not limited as far as use of aliphaticpolycarbonate having the increased molecular weight obtained by theaforementioned method is satisfied, and the reaction is performed at thetemperature in the range of the melting point of an aromatic polyesterconstituting the hard segment to the melting point +30° C. In thisreaction, the concentration of an active catalyst is arbitrarily setdepending on the temperature at which the reaction is performed. Thatis, since a transestrification reaction and depolymerization proceedrapidly at the higher reaction temperature, it is desirable that theconcentration of the active catalyst in the system is low, and it isdesirable that the active catalyst is present at some extent of theconcentration at the lower reaction temperature.

As the catalyst, a normal catalyst, for example, one or two or morekinds of titanium compounds such as titanium tetrabutoxide and potassiumoxalate titanate, and tin compounds such as dibutyltin oxide, andmonohydroxybutyltin oxide may be used. The catalyst may be present inthe polyester or the polycarbonate in advance and, in that case, it isnot necessary to add the catalyst newly. Further, the catalyst in thepolyester or the polycarbonate may be partially or substantiallycompletely inactivated in advance by an arbitrary method. For example,when titanium tetrabutoxide is used as the catalyst, the catalyst isinactivated by adding a phosphorus compound such as phosphorous acid,phosphoric acid, triphenyl phosphate, tristriethylene glycol phosphate,orthophosphoric acid, carbetoxydimethyldiethyl phosphonate, triphenylphosphite, trimethyl phosphate, and trimethyl phosphite, being notlimiting.

The reaction may be performed by arbitrarily determining a combinationof the reaction temperature, the catalyst concentration and the reactiontime. That is, its suitable value of the reaction condition fluctuatesdepending on a variety of factors such as the kind and the amount ratioof the hard segment and the soft segment used, a shape of an apparatusused, and stirring situation.

The optimal value of the reaction condition is, for example, the casewhere when the melting point of the resulting block copolymerizedpolyester (polyester-polycarbonate type thermoplastic polyesterelastomer) and the melting point of a polyester used as the hard segmentare compared, the difference thereof is 2° C. to 60° C. When the meltingpoint difference is less than 2° C., both segments have not been mixedor/and reacted, and the resulting polymer exhibits inferior elasticityperformance. On the other hand, when the melting point differenceexceeds 60° C., since the transesterification reaction proceedsremarkably, blocking property of the resulting polymer is reduced, andcrystallizability and elasticity performance are reduced.

For example, using polybutylene terephthalate as a polyester constructedof aromatic dicarboxylic acid and aliphatic or alicyclic diol, thepolybutylene terephthalate, and aliphatic polycarbonate consisting of1,6-hexanediol having the increased molecular weight are charged intothe reaction can at once at predetermined amounts, oxygen in thereaction can is removed with an inert gas, and the pressure in thereaction can is reduced. The pressure in the reaction can is preferably400 Pa or lower, more preferably 270 Pa or lower, further preferably 140Pa or lower. The mixture is stirred while maintaining the reducedpressure degree, the temperature is gradually raised, and a reactionproceeds at the temperature higher than the melting point ofpolybutylene terephthalate by 5 to 40° C., while dissolving thereactants. The temperature difference is more preferably a 7 to 35° C.higher temperature, further preferably a 10 to 30° C. highertemperature. When the temperature difference is smaller than 5° C.,since polybutylene terephthalate is solidified, and it cannot beuniformly mixed, there is a possibility that quality of the resultingthermoplastic polyester elastomer fluctuates. On the other hand, whenthe temperature difference is greater than 40° C., since the reactionproceeds too rapidly, the reaction is randomized, and a thermoplasticpolyester elastomer poor in heat resistance is made. The reaction timeis preferably 360 minutes or shorter, more preferably 360 minutes orshorter, further preferably 240 minutes or shorter. When the reactiontime is too long, a production cycle is extended, and this becomes afactor for increase in the production cost. At the timepoint when eachraw material becomes uniform, the reaction is completed, stirring isstopped, and a molten polyester-polycarbonate type thermoplasticpolyester elastomer is taken out through an outlet at a lower part ofthe reaction can, cooled to solidify, and cut with a chip cutter such asa strand cutter to obtain chips of a polyester-polycarbonate typethermoplastic polyester.

It is desirable to inactivate the catalyst remaining in the moltenmixture obtained by the reaction as completely as possible by anarbitrary method. When the catalyst remains more than necessary, atransesterification reaction further proceeds at compounding or atmolding, and it is thought that physical property of the resultingpolymer fluctuates.

The present inactivation reaction is performed by, for example, theaforementioned manner, that is, by adding a phosphorus compound such asphosphorous acid, phosphoric acid, triphenyl phosphate, tristriethyleneglycol phosphate, orthophosphoric acid, carbetoxydimethyldiethylphosphonate, triphenyl phosphite, trimethyl phosphate, and trimethylphosphite, being not limiting.

The polyester-polycarbonate type thermoplastic polyester elastomer ofthe present invention may contain tri- or-more functional polycarboxylicacid or polyol only at the small amount. For example, trimelliticanhydride, benzophenonetetracarboxylic acid, trimethylolpropane, orglycerin can be used.

In the present invention, in addition to the aforementioned two steps,for example, other steps such as a step of storing or drying aliphaticpolycarbonate having the increased molecular weight obtained in the step1, a step of producing, melting or drying an aromatic polyester to becharged into the step 2, a step of drying, increasing a viscosity of, orcompounding and the like the polyester-polycarbonate type thermoplasticpolyester elastomer obtained in the step 2, may be combined. Acombination of the steps can be arbitrarily set as far as inclusion ofthe step 1 and the step 2 is satisfied.

In the present invention, when the aforementioned requirement issatisfied, for example, the shape, the volume and the number of reactionapparatuses in which the steps are performed are not limited.

For example, the number of the reaction tank is one, and both of thestep 1 and the step 2 may be sequentially conducted in the one reactiontank. However, when both reactions are sequentially conducted in the onereaction tank, since variation of quality of the polyester-polycarbonatetype thermoplastic polyester elastomer in each production at repetitiveproduction is increased by influence of a kettle residue remaining inthe reaction tank when production is conducted by repetition, it is apreferable embodiment that the step 1 and the step 2 are conducted inseparate reaction tanks.

It is necessary that a structure of the reaction tank has at least astirrer for stirring reactants and the function of heating thereactants. Since both of the step 1 and the step 2 can promote thereaction by the reduced pressure in some cases, it is preferable thatthe reaction system is connected to a reduced pressure system. Asdescribed above, as a production apparatus by a batch method of ageneral-use polyester, a form that a transesterifiction reaction or anestrification reaction, and a polycondensation reaction are generallyconducted in separate reaction tanks is used, and since the structurehas the function, it is one of preferable embodiments that the reactionis conducted using an apparatus for producing a general-use polyester.

In the present invention, a combination of the step 1 and the step 2 isnot limited in other requirements as far as conduct of the step 2 afterthe step 1 is satisfied. For example, the step 1 and the step 2 may becontinuously performed, or may be performed discontinuously.

For example, the following conduct methods are exemplified, being notlimiting.

1. A method of first charging an aliphatic polycarbonate diol and achain extender using one reaction tank, performing raw materialmolecular weight up which is a reaction of the step 1, charging anaromatic polyester after completion of the reaction, subsequentlycontinuing heating and stirring, and performing a blocking reaction ofthe step 2 to obtain a polyester-polycarbonate type thermoplasticpolyester elastomer.

2. A method of, in two reaction tanks in which a reaction tank forconducting the step 1 and a reaction tank for performing the step 2 areconnected, charging an aliphatic polycarbonate diol and a chain extenderinto a first reaction tank, performing a reaction of the step 1,transferring the resulting reaction product to a second reaction tank,charging aromatic polyester chips into the second reaction tank, andheating and stirring the mixture to perform a blocking reaction toobtain a polyester-polycarbonate type thermoplastic polyester elastomer.

3. A method of melting an aromatic polyester in a second reaction tank,transferring aliphatic polycarbonate, a molecular weight of which hasbeen increased in the first reaction tank, to a second reaction tankwith the molten aromatic polyester charged therein, and performing ablocking reaction, in the method of 2.

4. A method of charging, for example, an aromatic polyester which hasbeen melted with a melt extruder into a second reaction tank, in themethod of 2. An order of charging the aliphatic polycarbonate and themolten aromatic polyester into the second reaction tank in this case isnot limited. Simultaneous charging, or a sequential method of chargingany one of them, and charging the other may be used.

5. A method of providing an apparatus for producing an aromaticpolyester, and charging the aromatic polyester in the molten stateproduced by the apparatus for producing the aromatic polyester, in themethod of 3.

6. A method of preparing two reaction tanks, performing a reaction ofthe step 1 using one reaction tank, taking out the reaction product,taking out aliphatic polycarbonate with the increased molecular weightto convert into a solid, charging the solid aliphatic polycarbonate withthe increased molecular weight and an aromatic polyester into the otherreaction tank, and performing a blocking reaction of the step 2 toobtain a polyester-polycarbonate type thermoplastic polyester elastomer.

7. A method of preparing three reaction tanks, performing a reaction ofthe step 1 using one of the reaction tanks, taking out the reactionproduct, transferring aliphatic polycarbonate with the increasedmolecular weight in the molten state to a second tank, and storing thepolycarbonate under the nitrogen atmosphere, and performing a blockingreaction of the step 2 in a third reaction tank to obtain apolyester-polycarbonate type thermoplastic polyester elastomer.

8. A method of providing a compounding tank in which an aliphaticpolycarbonate diol and a chain extender are blended, in addition to thereaction tanks used in the aforementioned methods, charging an aliphaticpolycarbonate diol and a chain extender into the compounding tank,compounding a composition for performing a reaction of the step 1, andcharging this into a reaction tank in which a reaction of the step 1 isperformed in the methods of 1 to 6.

In the polyester-polycarbonate type thermoplastic polyester elastomer ofthe present invention obtained by the aforementioned methods, it isimportant that, when a cycle of raising the temperature of thepolyester-polycarbonate type thermoplastic polyester elastomer from roomtemperature to 300° C. at the temperature raising rate of 20° C./minusing a differential scanning calorimeter, retaining the elastomer at300° C. for 3 minutes, and lowering the temperature to room temperatureat the temperature lowering rate of 100° C./min is repeated three times,the melting difference (Tm1−Tm3) between the melting point (Tm1)obtained by first measurement and the melting point (Tm3) obtained bythird measurement is 0 to 50° C. The melting point difference is morepreferably 0 to 40° C., further preferably 0 to 30° C. The melting pointdifference is a measure of blocking property retainability of thepolyester-polycarbonate type thermoplastic polyester elastomer, and asthe temperature difference is smaller, blocking property retainabilityis more excellent. When the melting point difference exceeds 50° C.,blocking property retainability is deteriorated, and fluctuation ofquality at molding and processing becomes great, leading todeterioration of quality uniformity of molded articles, anddeterioration of recycle property.

By satisfying the aforementioned properties, the effect of excellentblocking property possessed by the polyester-polycarbonate typethermoplastic polyester elastomer of the present invention describedlater can be effectively utilized.

In the present invention, the hard segment consists of a polybutyleneterephthalate unit and the melting point of the polyester-polycarbonatetype thermoplastic polyester elastomer is preferably 200 to 225° C.,more preferably 205 to 225° C.

Further, in the present invention, the hard segment consists of apolybutylene naphthalate unit and the melting point of thepolyester-polycarbonate type thermoplastic polyester elastomer ispreferably 215 to 240° C., more preferably 220 to 240° C.

When the hard segment is a polybutylene terephthalate unit or apolybutylene naphthalate unit, it is economically advantageous becausecommercial polyesters such as polybutylene terephthalate or polybutylenenaphthalate may be used.

It is not preferable that the melting point of thepolyester-polycarbonate type thermoplastic polyester elastomer is belowthe above lower limit because its blocking property declines and heatresistance and mechanical properties of the polyester-polycarbonate typethermoplastic polyester elastomer are deteriorated. On the other hand,it is not preferable that the melting point is above the above upperlimit because compatibility between the hard segment and the softsegment becomes worse and mechanical properties of thepolyester-polycarbonate type thermoplastic polyester elastomer aredeteriorated.

The polyester-polycarbonate type thermoplastic polyester elastomer ofthe present invention has a polyester unit as the hard segment and analiphatic polycarbonate unit as the soft segment. An average of therepeating number of repeating units constituting one of the homopolymerstructure units is referred to as an average chain length and, in thistext, the value is calculated by using nuclear magnetic resonance (NMR)unless otherwise instructed.

Letting the average chain length of the hard segment to be x and anaverage chain length of the soft segment to be y when they arecalculated by using nuclear magnetic resonance (NMR), it is preferablethat the average chain length of the hard segment (x) is 5 to 20 andblocking property (B) calculated by the following equation (1):B=1/x+1/y  (1)is 0.11 to 0.45.

In the polyester-polycarbonate type thermoplastic polyester elastomer ofthe present invention, the average chain length of the polyester unitwhich is a hard segment constituent component is preferably 5 to 20,more preferably 7 to 18, further preferably 9 to 16.

In the polyester-polycarbonate type thermoplastic polyester elastomer ofthe present invention, the average chain length of a polyester unit inthe hard segment (x) is an important factor which determines blockingproperty of the polyester-polycarbonate type thermoplastic polyesterelastomer, and greatly influences on the melting point of thepolyester-polycarbonate type thermoplastic polyester elastomer. Ingeneral, as the average chain length of the polyester unit (x) isincreased, the melting point of the polyester-polycarbonate typethermoplastic polyester elastomer rises. In addition, the average chainlength of the polyester unit in the hard segment (x) is also a factorinfluencing on mechanical properties of the polyester-polycarbonate typethermoplastic polyester elastomer. When the average chain length of thepolyester unit in the hard segment (x) is smaller than 5, it is meantthat randomization proceeds and, therefore, heat resistance andmechanical properties such as a hardness, a tensile strength, and anelastic modulus is greatly deteriorated. When the average chain lengthof the polyester unit in the hard segment (x) is larger than 20,compatibility with aliphatic carbonate diol constituting the softsegment becomes worse to cause phase separation and, thereby, mechanicalproperties are greatly influenced, resulting in decrease in its strengthand elongation.

Blocking property (B) is preferably 0.11 to 0.45, more preferably0.13-0.40, further preferably 0.15 to 0.35. As this value becomeslarger, the blocking property declines. It is not preferable that theblocking property is larger than 0.45 because polymer characteristicsare deteriorated due to decline of the blocking property, for example,the melting point of the polyester-polycarbonate type thermoplasticpolyester elastomer declines, and the like. On the other hand, it is notpreferable that the blocking property is smaller than 0.11 becausecompatibility between the hard segment and the soft segment isdeteriorated, resulting in deterioration in mechanical properties suchas a strength and an elongation and flex resistance and the like of thepolyester-polycarbonate type thermoplastic polyester elastomer, andincrease in fluctuation of those mechanical properties.

Additionally, the blocking property is calculated by the followingequation (1).B=1/x+1/y  (1)

Based on the above relationship, the average chain length (y) of thesoft segment is preferably 4 to 15.

Only by satisfying the blocking property, both excellent heat resistanceand excellent mechanical properties can be simultaneously obtained.

A tensile strength at break of the polyester-polycarbonate typethermoplastic polyester elastomer of the present invention is 15 to 100MPa, preferably 20 to 60 MPa.

In addition, a flexural modulus of the polyester-polycarbonate typethermoplastic polyester elastomer of the present invention is preferably1000 MPa or lower, more preferably 800 MPa or lower, further preferably600 MPa or lower. It is not preferable that the flexural modulus is morethan 1000 MPa because flexibility of the polyester-polycarbonate typethermoplastic polyester elastomer is insufficient. The lower limit ispreferably 50 MPa or higher, more preferably 80 MPa or higher, furtherpreferably 100 MPa or higher. When it is lower than 50 MPa, thepolyester-polycarbonate type thermoplastic polyester elastomer is tooflexible to secure a strength of products.

In addition, in the polyester-polycarbonate type thermoplastic polyesterelastomer of the present invention, it is preferable that an elongationat break and a retention rate of the polyester-polycarbonate typethermoplastic polyester elastomer composition after heat-aging test andafter water-aging test evaluated by a method described in a section[Measurement methods] is 50% or higher and 80% or higher, respectively.

The polyester-polycarbonate type thermoplastic polyester elastomer ofthe present invention is molded from a melt by ordinary moldingtechniques such as injection molding, flat film extrusion, extrusionblow molding or co-extrusion.

In addition, various additives may be added to thepolyester-polycarbonate type thermoplastic polyester elastomer of thepresent invention, depending on purposes, to obtain a composition. Asadditives, known hindered phenol-type, sulfur-type, phosphorus-type,amine-type antioxidant, hindered amine-type, triazole-type,benzophenone-type, benzoate-type, nickel-type, salicyl-type and othertypes light stabilizers; antistatic agents; slipping agents; molecularweight modifiers such as peroxide and the like; compounds having areactive group such as an epoxy-type compound, an isocyanate-typecompound, a carbodiimide-type compound and the like; metal inactivationagents; organic or inorganic nucleating agents cores; neutralizers; acidretarder; antibacterial agents; fluorescent whitener; fillers; flameretardant; flame retardant assistants; organic or inorganic pigments;and others may be added.

Hindered phenol-type antioxidants which may be used in the presentinvention include 3,5-di-t-butyl-4-hydroxy-toluene,n-octadecyl-β-(4′-hydroxy-3′,5′-di-t-butylphenyl)propionate,tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane,1,3,5-trimethyl-2,4,6′-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene,calcium (3,5-di-t-butyl-4-hydroxy-benzyl-monoethyl-phosphate),triethyleneglycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate],pentaerythrityl-tetrakis[3-(3,5-di-t-butylanilino)-1,3,5-triazine,3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane,bis[3,3-bis(4′-hydroxy-3′-t-butylphenyl)butyric acid]glycol ester,triphenol, 2,2′-ethylidene bis(4,6-di-t-butylphenol),N,N′-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine,2,2′-oxamide bis[ethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],1,1,3-tris(3′,5′-di-t-butyl-4′-hydroxybenzyl)-S-triazine-2,4,6(1H,3H,5H)-trione,1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,3,5-di-t-butyl-4-hydroxyhydrocinnamic acid triester with1,3,5-tris(2-hydroxyethyl)-S-triazine-2,4,6 (1H,3H,5H),N,N-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamide),3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecaneand the like.

Sulfur-type antioxidants which may be used in the present inventioninclude dilauryl-3,3′-thiodipropionate,dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate,lauryl stearyl-3,3′-thiodipropionate, dilauryl thiodipropionate,dioctadecyl sulfide, pentaerythritol-tetra(β-lauryl-thiopropionate)ester and the like.

Phosphorus-type antioxidants which may be used in the present inventioninclude tris(mixed, mono- and di-Norylphenyl)phosphite,tris(2,3-di-t-butylphenyl)phosphite, 4,4′-butylidenebis(3-methyl-6-t-butylphenyl-di-tridecyl)phosphite,1,1,3-tris(2-methyl-4-di-tridecylphosphite-5-t-butylphenyl)butane,tris(2,4-di-t-butylphenyl)phosphite,bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite,tetrakis(2,4-di-t-butylphenyl)-4,4′-biphenylene phosphite,bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol-diphosphite,tetrakis(2,4-di-t-butylphenyl) 4,4′-biphenylene diphosphonite, triphenylphosphite, diphenyldecyl phosphite, tridecyl phosphite, trioctylphosphite, tridocecyl phosphite, trioctadecyl phosphite, trinonylphenylphosphite, tridocecyl trithiophosphite and the like.

Amine-type antioxidants which may be used in the present inventioninclude amines such as N,N-diphenylethylenediamine,N,N-diphenylacetoamidine, N,N-diphenylformamidine, N-phenylpiperidine,dibenzylethylenediamine, triethanolamine, phenothiazine,N,N′-di-sec-butyl-p-phenylenediamine,4,4′-tetramethyl-diaminodiphenylmethane, p,p′-dioctyl-diphenylamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine, phenyl-α-naphthylamine,phenyl-β-naphthylamine, 4,4′-bis(4-α,α-dimethylbenzyl)diphenylamine andthe like; their derivatives; reaction products of amine and aldehyde;reaction products of amine and ketone.

Hindered amine-type light stabilizers which may be used in the presentinvention include polycondensates of dimethyl succinate with1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine,poly[[6-(1,1,3,3-tetrabutyl)imino-1,3,5-triazin-2,4-diyl]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imyl]],bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-n-butylmalonate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate,bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, polycondensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and1,2-dibromoethane,poly[(N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine)-(4-molpholino-1,3,5-triazin-2,6-diyl)-bis(3,3,5,5-tetramethylpiperazinone)],tris(2,2,6,6-tetramethyl-4-piperidyl)-docecyl-1,2,3,4-butanetetracarboxylate,tris(1,2,2,6,6-pentamethyl-4-piperidyl)-docecyl-1,2,3,4-butanetetracarboxylate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,1,6,11-tris[{4,6-bis(N-butyl-N-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino-1,3,5-triazin-2-yl)amino}undecane,1-[2-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-tetramethylpiperidine,8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro[4,5]undecane-2,4-dione,4-benzoyloxy-2,2,6,6-tetramethylpiperidine,N,N′-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-triazinecondensate.

Benzophenone-type, benzotriazole-type, triazole-type, nickel-type andsalicyl-type light stabilizers which may be used in the presentinvention include light stabilizers such as2,2′-di-hydroxy-4-methoxybenzophenone,2-hydroxy-4-n-octyloxybenzophenone, p-t-butylphenyl salicylate,2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate,2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(2′-hydroxy-3′,5′-di-t-amyl-phenyl)benzotriazole,2-[2′-hydroxy-3′,5′-bis(α,α-dimethylbenzylphenyl)benzotriazole,2-(2′-hydroxy-3′-t-butyl-5′-methylphenyl)-5-chlorobenzoazotriazole,2-(2′-hydroxy-3′,5′-di-t-butylphenyl)-5-chlorobenzothiazole,2,5-bis[5′-t-butylbenzooxazolyl-(2)]-thiophene, nickel bis(monoethyl3,5-di-t-butyl-4-hydroxybenzylphosphate), a mixture of bisanilide2-ethoxy-5-t-butyl-2′-ethyloxalate 85 to 90% and bisanilide2-ethoxy-5-t-butyl-2′-ethyl-4′-t-butyloxalate 10 to 15%,2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole,bisanilide 2-ethoxy-2′-ethyloxalate,2-[2′-hydroxy-5′-methyl-3′-(3″,4″,5″,6″-tetrahydrophthalimido-methyl)phenyl]benzotriazole,bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane,2-(2′-hydroxy-5′-t-octylphenyl)benzotriazole,2-hydroxy-4-i-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone,2-hydroxy-4-octadecyloxybenzophenone, phenyl salicylate and the like.

Slipping agents which may be used in the present invention includehycrocarbon-type, fatty acid-type, fatty acid amide-type, ester-type,alcohol-type, metal soap-type, natural wax-type, silicone-type,fluorine-type compounds and the like. Specifically, included areslipping agents such as liquid paraffin, synthetic paraffin, synthetichard paraffin, synthetic isoparaffin petroleum hydrocarbon, chlorinatedparaffin, paraffin wax, microcrystalline wax, low-polymerization-degreepolyethylene, fluorocarbon oil, fatty acid compounds having a carbonnumber of 12 or more such as lauric acid, myristic acid, palmitic acid,stearic acid, arachidic acid, behenic acid and the like, saturated orunsaturated aliphatic amides such as having a carbon number of 3 to 30,hexylamide, octylamide, stearylamide, palmitylamide, oleylamide,erucylamide, ethylene bisstearylamide, laurylamide, behenylamide,methylene bisstearylamide and ricinol amide, and their derivatives, alower alcohol ester of fatty acid, a polyhydric alcohol ester of fattyacid, a polyglycol ester of fatty acid, a fatty alcohol ester of fattyacid such as butyl stearate, hydrogenated castor oil, ethylene glycolmonostearate and the like, cetyl alcohol, stearyl alcohol, ethyleneglycol, polyethylene glycols having a molecular weight of 200 to 10000or higher, polyglycerol, carnauba wax, candelilla wax, montan wax,dimethylsilicone, silicone gum, ethylene tetrafluoride and the like. Inaddition, metal salts of a compound containing linear saturated fattyacid, an acid at a side chain, sinolic acid, wherein the metal isselected from Li, Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn and Pb may be alsoincluded.

Fillers which may be used in the present invention include oxides suchas magnesium oxide, aluminium oxide, silicon oxide, calcium oxide,titanium oxide (rutile type, anatase type), chromium oxide (trivalent),iron oxide, zinc oxide, silica, diatomaceous earth, alumina fiber,antimony oxide, barium ferrite, strontium ferrite, beryllium oxide,pumice, pumice balloon and the like, basic substances or hydroxides suchas magnesium hydroxide, aluminium hydroxide, basic magnesium carbonateand the like, salts of carbonic acid such as magnesium carbonate,calcium carbonate, barium carbonate, ammonium carbonate, calciumsulfite, dolomite, dowsonite and the like, salts of sulfurous acid orsulfuric acid such as calcium sulfate, barium sulfate, ammonium sulfate,calcium sulfite, basic magnesium sulfate and the like, salts of silicicacid such as sodium silicate, magnesium silicate, aluminium silicate,potassium silicate, calcium silicate, talc, clay, mica, asbestos, glassfibers, montmorillonite, glass balloons, glass beads, pentonite and thelike, kaolin (clay for earthen wares), pearlite, iron powder, copperpowder, lead powder, aluminium powder, tungsten powder, molybdenumsulfide, carbon black, boron fibers, silicon carbide fibers, brassfibers, potassium titanate, lead titanate zirconate, zinc borate,aluminium borate, barium metaborate, calcium borate, sodium borate, andothers.

Flame retardant assistants which may be used in the present inventioninclude antimony trioxide, antimony tetraoxide, antimony pentaoxide,sodium pyroantimonate, tin dioxide, zinc metaborate, aluminiumhydroxide, magnesium hydroxide, zirconium oxide, molybdenum oxide, redphosphorus compounds, ammonium polyphosphate, melamine cyanurate,ethylene tetrafluoride and the like.

Compounds having a triazine group and/or their derivatives which may beused in the present invention include melamine, melamine cyanurate,melamine phosphate, guanidine sulfamate and the like.

In phosphorus compounds which may be used in the present invention,inorganic phosphorus compounds include red phosphorus compounds,ammonium polyphosphate and the like. Red phosphorus compounds includeresin-coated red phosphorus, complex compounds with aluminium, and thelike. Organic phosphorus compounds include phosphoric acid ester,melamine phosphate and the like. As phosphoric acid esters, phosphates,phosphonates and phosphinates such as trimethyl phosphate, triethylphosphate, tributyl phosphate, trioctyl phosphate, trioctyl phosphinate,tributoxyethyl phosphate, octyldiphenyl phosphate, tricresyl phosphate,cresyl diphenyl phosphate, triphenyl phosphate, trixylenyl phosphate,trisisopropylphenyl phosphate, diethylN,N-bis(2-hydroxyethyl)aminomethyl phosphonate,bis(1,3-phenylenediphenyl)phosphate; aromatic condensed phosphoric acidester such as 1,3-[bis(2,6-dimethylphenoxy)phosphenyloxy]benzene,1,4-[bis(2,6-dimethylphenoxy)phosphenyloxy]benzene; and others arepreferable from a view point of hydrolysis resistance, thermal stabilityand flame resistance.

These additives may be compounded by using kneading machines such asheating rolls, extruders, Banbury mixers and the like. These additivesmay be added to or mixed with oligomers before transesterification whenpreparing a polyester-polycarbonate type thermoplastic polyesterelastomer resin composition or before polycondensation.

EXAMPLE

The present invention will be specifically explained below withreferring to Examples and Comparative Examples, but is not limited tothem. Additionally, each measurement in the present invention wascarried out according to the following manners.

-   (1) Reduced Viscosity of Polyester-Polycarbonate Type Thermoplastic    Polyester Elastomer

In 25 mL of a mixed solvent (phenol/tetrachloroethane=60/40 (massratio)) was dissolved 0.05 g of a polyester-polycarbonate typethermoplastic polyester elastomer, and the viscosity was measured at 30°C. using an Ostwald viscometer.

-   (2) Melting Point of Polyester-Polycarbonate Type Thermoplastic    Polyester Elastomer (Tm)

A polyester-polycarbonate type thermoplastic polyester elastomer driedunder reduced pressure at 50° C. for 15 hours was subjected tomeasurement on a differential scanning carolimeter DSC-50 (manufacturedby SHIMADZU CORPORATION) at the heating rate of 20° C./min. from roomtemperature. The temperature at an endotherm peak due to melting wasdefined as the melting point.

Additionally, measurement samples were subjected to measurements byplacing 10 mg in an aluminium pan (P/N 900793.901, manufactured by TAINSTRUMENTS) and by sealing it with an aluminium lid (P/N 900794.901,manufactured by TA INSTRUMENTS) under argon atmosphere.

-   (3) Tensile Strength and Elongation at Break of    Polyester-Polycarbonate Type Thermoplastic Polyester Elastomer

A tensile strength and an elongation at break of apolyester-polycarbonate type thermoplastic polyester elastomer weremeasured according to JIS K 6251. Test pieces of #3 dumbbell type wereprepared by injection molding into flat plates having the dimension of100 mm×100 mm×2 mm on an injection molding machine (model-SAV,manufactured by SANJO SEIKI Co., Ltd.) at the cylinder temperature of(Tm+20° C.) and at the mold temperature of 30° C. and by stamping theflat plates.

-   (4) Flexural Modulus

A flexural modulus of a polyester-polycarbonate type thermoplasticpolyester elastomer was measured according to ASTM D790.

-   (5) Heat-Aging Resistance (Retention Rate of Elongation at Break    after Heat-Aging Test)    <Preparation of Test Piece>

In a drum tumbler were placed 100 parts by mass of pellets of apolyester-polycarbonate type thermoplastic polyester elastomer driedunder reduced pressure at 100° C. for 8 hours, 0.35 parts by mass of amultifunctional epoxy compound, 0.2 parts by weight of a catalyst, and1.2 parts by mass of a stabilizer, and they were mixed at roomtemperature for 30 minutes. The mixture was melted and kneaded at thetemperature of (Tm+20° C.) and extruded in a strand by using a 40-mmφco-rotating double screw extruder with a vent. The strand was cut intochips with water cooling. The chips were dried under reduced pressure at100° C. to obtain chips of the polyester-polycarbonate typethermoplastic polyester elastomer composition.

Test pieces of #3 dumbbell type were prepared by injection molding thepolyester-polycarbonate type thermoplastic polyester elastomer into flatplates having the dimension of 100 mm×100 mm×2 mm using an injectionmolding machine (model-SAV, manufactured by SANJO SEIKI Co., Ltd.) atthe cylinder temperature of (Tm+20° C.) and at the mold temperature of30° C. and by stamping the flat plates.

<Dry-Heating Treatment, Evaluation of Ability to Retain Elongation atBreak>

The test pieces obtained in the above were treated in a Gear type hotair dryer at 180° C. and for 1000 hours and, then, an elongation atbreak was measured according to JIS K 6251. Also for the untreated testpieces, an elongation at break was measured in the same manner tocalculate the retention rate of the elongation at break afterdry-heating treatment.

-   (6) Water-Aging Resistance (Retention Rate of Elongation at Break    after Water-Aging Test)    <Preparation of Test Piece>

Test pieces were prepared by the same manner described in the method formeasuring heat-aging resistance.

<Boiling-Water Treatment, Evaluation of Ability to Retain Elongation atBreak>

The test pieces were treated in boiling water at 100° C. and for 2 weeksand, then, an elongation at break was measured according to JIS K 6251.Also for the untreated test pieces, an elongation at break was measuredin the same manner to calculate the retention rate of the elongation atbreak after boiling-water treatment.

-   (7) Average Chain Length and Blocking Property of Hard Segment and    Soft Segment (when the Glycol Component in Polyester is Butanediol    and the Glycol in Aliphatic Polycarbonate Diol is Aliphatic Diol    Having a Carbon Number of 5-12)    <NMR Measurement>-   Equipment: Fourier-Transform Nuclear Magnetic Resonance    System (ADVANCE 500 manufactured by BRUKER)

Solvent: Deuteriated chloroform

Concentration of sample solution: 3-5 vol %

¹H resonance frequency: 500.13 MHz

Flip angle of detection pulse: 45°

Data sampling rate: 4 seconds

Delay time: 1 second

Integration number: 50-200 times

Measurement temperature: Room temperature

<Calculation Method>

The H-NMR integration value. (arbitrary unit) of a peak for methylenegroups next to oxygen atoms, of butanediol in a linkage of aromaticdicarboxylic acid-butane diol-aromatic dicarboxylic acid was defined asA.

The H-NMR integration value (arbitrary unit) of a peak for a methylenegroup next to an oxygen atom closer to carbonic acid, of butanediol in alinkage of aromatic dicarboxylic acid-butanediol-carbonic acid wasdefined as C.

The H-NMR integration value (arbitrary unit) of a peak for a methylenegroup next to an oxygen atom closer to aromatic dicarboxylic acid, ofhexanediol in a linkage of aromatic dicarboxylic acid-aliphatic diolhaving a carbon number of 5 to 12-carbonic acid was defined as B.

The H-NMR integration value (arbitrary unit) of a peak for methylenegroups next to an oxygen atom, of aliphatic diol having a carbon numberof 5 to 12 in a linkage of carbonic acid-aliphatic diol having a carbonnumber of 5 to 12-carbonic acid was defined as D.

The hard segment average chain length (x) is defined as follows.x=(((A/4)+(C/2))/((B/2)+(C/2)))×2

The soft segment average chain length (y) is defined as follows.y=(((D/4)+(B/2))/((B/2)+(C/2)))×2.

Blocking property (B) is calculated by the following equation (1) byusing x and y values obtained by the above equations. Smaller B valuesindicate higher blocking properties.B=1/x+1/y  (1)(9) Blocking Property Retainability

Measurement samples were prepared by weighing 10 mg of apolyester-polycarbonate type thermoplastic polyester elastomer driedunder reduced pressure at 50° C. and for 15 hours into an aluminium pan(P/N 900793.901, manufactured by TA INSTRUMENTS) and by sealing it withan aluminium lid (P/N 900794.901, manufactured by TA INSTRUMENTS). Themeasurement pan was heated on a differential scanning carolimeter DSC-50(manufactured by SHIMADZU CORPORATION) under nitrogen atmosphere fromroom temperature to 300° C. at the heating rate of 20° C./min.,maintained at 300° C. for 3 minutes and, then, the pan was removed torapidly cool by dipping into liquid nitrogen. The sample was removedfrom liquid nitrogen and allowed to stand at room temperature for 30minutes. The measurement pan was set on the differential scanningcalorimeter and, after allowing to stand 30 minutes at room temperature,it was heated again from room temperature to 300° C. at the heating rateof 20° C./min. After this cycle was repeated three times, the meltingpoint difference (Tm1−Tm3) between the melting point obtained in firstmeasurement (Tm1) and the melting point obtained in third measurement(Tm3) was calculated. The melting point difference was defined asblocking property retainability. As the difference becomes smaller,blocking property retainability is more excellent.

Based on the melting point difference, blocking property retainabilitywas judged using the following criteria:

-   ⊚: Melting Point Difference is 0—lower than 30° C.,-   ◯: Melting Point Difference is 30—lower than 40° C.-   Δ: Melting Point Difference is 40—lower than 50° C.-   X: Melting Point Difference is 50° C. or higher.-   (9) Molecular Weight of Aliphatic Polycarbonate Diol

An aliphatic polycarbonate diol sample was dissolved in deuteriatedchloroform (CDCl₃) and H-NMR of end groups was measured in the samemanner described in (8) and its molecular weight was calculated by thefollowing equation:Molecular weight=1000000/((end group concentration (eq/ton))/2)

-   (10) Concentration of Hydroxyl Endo Group of Aromatic Polyester

In 0.1 ml of deuteriated hexafluoroisopropanol (HFIP-d2)+deuteriatedchloroform CDCl₃(1+1) was dissolved 15 ml of a sample, this was dilutedwith 0.42 ml of CDCl₃ containing 0.0125M triethylamine (TEA), 30 μl ofheavy pyridine was added, and H-NMR was measured according to the methoddescribed in (7).

-   (11) Number Average Molecular Weight (Mn) of Aromatic Polyester

The number average molecular weight (Mn) of an aromatic polyester wascalculated according to the following equation using the reducedviscosity (ηsp/c) in the same manner as the above reduced viscositymeasurement method for the thermoplastic polyester elastomer.ηsp/c=1.019×10⁻⁴ ×Mn ^(0.8929−0.0167)

Example 1

Into an estrification reaction tank of a general-use polyesterproduction apparatus consisting of one estrification reaction tank andtwo polycondensation reaction tanks were charged 100 parts by mass ofaliphatic polycarbonate diol (carbonate diol UH-CARB200, manufactured byUbe Industries, Ltd., molecular weight 2000, 1,6-hexanediol type) and8.6 parts by mass of diphenyl carbonate, and materials werehomogeneously mixed, and transferred to an initial polycondensationreaction tank. After completion of transfer, the temperature of theinitial polycondensation reaction tank was gradually raised, and thetank was heated at the temperature of 205° C. Thereafter, the pressurewas gradually reduced, followed by a reaction at 130 Pa to perform areaction of increasing the molecular weight of aliphatic polycarbonatediol. After two hours, the content was transferred to a laterpolycondensation reaction tank. The molecular weight of aliphaticpolycarbonate at transfer was 10000. The later polycondensation reactiontank was charged with 236.4 parts by weight of chips of polybutyleneterephthalate (PBT) having the number average molecular weight of 30000,and the moisture amount of 80 ppm, and the temperature was graduallyraised to 245° C., while stirring. The pressure in a can was retained at130 Pa and, after the internal temperature reached 245° C., it wasconfirmed that the resin became transparent in one hour, to complete ablocking reaction. The content was removed, and cooled to obtain apolyester-polycarbonate type thermoplastic polyester elastomer. Eachphysical property of the resulting polyester-polycarbonate typethermoplastic polyester elastomer was measured. Results are shown inTable 1. The polyester-polycarbonate type thermoplastic polyesterelastomer obtained in the present Example exhibited all good properties,and was of high quality.

Example 2

According to the same manner as that of Example 1 except that thecharging amount of diphenyl carbonate was changed to 9.6 parts by massin the method of Example 1, to obtain aliphatic polycarbonate having theincreased number average molecular weight of 20000, and the blockingreaction time was changed to 1.5 hours, a polyester-polycarbonate typethermoplastic polyester elastomer of Example 2 was obtained. Results areshown in Table 1. The polyester-polycarbonate type thermoplasticpolyester elastomer obtained in the present Example had equivalentquality to that of the polyester-polycarbonate type thermoplasticpolyester elastomer obtained in Example 1, and was of high quality.

Example 3

According to the same manner as that of Example 2 except that thecharging amount of diphenyl carbonate was changed to 10.5 parts by mass,and the reaction time for increasing the molecular weight of aliphaticpolycarbonate diol was changed to 1.5 hours, to obtain aliphaticpolycarbonate having the increased number average molecular weight of50000, and chips were changed to chips of polybutylene terephthalate(PBT) having the number average molecular weight of 20000 in the methodof Example 2, a polyester-polycarbonate type thermoplastic polyesterelastomer of Example 3 was obtained. Results are shown in Table 1. Thepolyester-polycarbonate type thermoplastic polyester elastomer obtainedin the present Example had equivalent quality to that of thepolyester-polycarbonate type thermoplastic polyester elastomer obtainedin Example 2, and was of high quality.

Example 4

According to the same manner as that of Example 1 except that thealiphatic copolymerized polycarbonate diol was changed to aliphaticcopolymerized polycarbonate diol (polycarbonate diol T5652, manufacturedby Asahi Kasei Chemicals Corporation, molecular weight 2000, copolymerof 1,6-hexanediol and caprolactone, amorphous in the method of Example1), a polyester-polycarbonate type thermoplastic polyester elastomer ofExample 4 was obtained. Results are shown in Table 1.

The polyester-polycarbonate type thermoplastic polyester elastomerobtained in the present Example had equivalent quality to that of thepolyester-polycarbonate type thermoplastic polyester elastomer obtainedin Example 1, and was of high quality.

Example 5

According to the same manner as that of Example 1 except that chips ofpolybutylene naphthalate (PBN: naphthalate part was 2,6 body) having thenumber average molecular weight of 30000 were used in place of PBTchips, and the blocking reaction temperature was changed to 265° C. inthe method of Example 1, a polyester-polycarbonate type thermoplasticpolyester elastomer of Example 5 was obtained. Results are shown inTable 1.

The polyester-polycarbonate type thermoplastic polyester elastomerobtained in the present Example had equivalent blocking property andblocking property retainability to those of the polyester-polycarbonatetype thermoplastic polyester elastomer obtained in Example 1, and hadthe higher melting point than that of the polyester-polycarbonate typethermoplastic polyester elastomer obtained in Example 1, and was ofhigher quality.

Example 6

According to the same manner as that of Example 1 except that chargingof raw materials was changed to 100 parts by mass of aliphaticpolycarbonate diol (carbonate diol UH-CARB200, manufactured by UbeIndustries, Ltd., molecular weight 2000, 1,6-hexanediol type) and 10.1parts by mass of 4,4′-diphenylmethane diisocyanate, and a reaction ofincreasing the molecular weight of aliphatic polycarbonate diol wasperformed at 180° C. for 2 hours under the nitrogen atmosphere, apolyester-polycarbonate type thermoplastic polyester elastomer ofExample 6 was obtained. Results are shown in Table 1. A molecular weightof aliphatic polycarbonate at transfer to the blocking reaction tank was10000.

The polyester-polycarbonate type thermoplastic polyester elastomerobtained in the present Example had equivalent quality to that of thepolyester-polycarbonate type thermoplastic polyester elastomer obtainedin Example 1, and was of high quality.

Example 7

According to the same manner as that of Example 1 except that chargingof raw materials was changed to 100 parts by mass of aliphaticpolycarbonate diol (carbonate diol UH-CARB200, manufactured by UbeIndustries, Ltd., molecular weight 2000, 1,6-hexanediol type) and 8.7parts by mass of pyromellitic dianhydride, and a reaction of increasingthe molecular weight of aliphatic polycarbonate diol was performed atthe temperature of 205° C. and 130 Pa for 2 hours, apolyester-polycarbonate type thermoplastic polyester elastomer ofExample 7 was obtained. Results are shown in Table 1. The molecularweight of aliphatic polycarbonate at transfer to the blocking reactiontank was 10000.

The polyester-polycarbonate type thermoplastic polyester elastomerobtained in the present Example had equivalent quality to that of thepolyester-polycarbonate type thermoplastic polyester elastomer obtainedin Example 1, and was of high quality.

Example 8

Into an esterification reaction tank of a general-use polyesterproduction apparatus consisting of one esterification reaction tank andtwo polycondensation reaction tanks were charged 100 parts by mass ofaliphatic polycarbonate diol (carbonate diol UH-CARB200, manufactured byUbe Industries, Ltd., molecular weight 2000, 1,6-hexanediol type) and9.6 parts by mass of diphenyl carbonate, and materials werehomogeneously mixed, and transferred to an initial polycondensationreaction tank. After completion of transfer, the temperature of theinitial polycondensation reaction tank was gradually raised, and themixture was heated at 205° C. Thereafter, a pressure was graduallyreduced, followed by a reaction at 130 Pa to perform a reaction ofincreasing the molecular weight of aliphatic polycarbonate diol. Aftertwo hours, the content was transferred to a later polycondensationreaction tank. The molecular weight of polycarbonate at transfer was20000. Into the later polycondensation reaction tank was charged 134.3parts by mass of chips of polybutylene terephthalate (PBT) having thenumber average molecular weight of 30000 and the moisture amount of 80ppm, and the temperature was gradually raised to 230 to 240° C. whilestirring. The pressure in the can was retained at 130 Pa and, after theinternal temperature reached 240° C., it was confirmed that the resinbecame transparent in one hour, and the blocking reaction was completed.The content was removed, and cooled to obtain a polyester-polycarbonatetype thermoplastic polyester elastomer. Each physical property of theresulting polyester-polycarbonate type thermoplastic polyester elastomerwas measured, and results are shown in Table 2. Thepolyester-polycarbonate type thermoplastic polyester elastomer obtainedin the present Example had all good properties, and was of high quality.

Example 9

According to the same manner as that of Example 8 except that chargingwas changed to 100 parts by mass of aliphatic polycarbonate, diol(carbonate diol UH-CARB200, manufactured by Ube Industries, Ltd.,molecular weight 2000, 1,6-hexanediol type) and 10.0 parts by mass ofdiphenyl carbonate, and the amount of chips of polybutyleneterephthalate (PBT) was changed to 101.3 parts by mass in the method ofExample 8, a polyester-polycarbonate type thermoplastic polyesterelastomer of Example 9 was obtained. Results are shown in Table 2. Thepolyester-polycarbonate type thermoplastic polyester elastomer obtainedin the present Example had all good properties, and was of high quality.

Example 10

Into an esterification reaction tank of a general-use polyesterproduction apparatus consisting of one esterification reaction tank andtwo polycondensation reaction tanks were charged 100 parts by mass ofaliphatic polycarbonate diol (carbonate diol UH-CARB200, manufactured byUbe Industries, Ltd., molecular weight 2000, 1,6-hexanediol type) and9.6 parts by mass of diphenyl carbonate, and materials werehomogeneously mixed, and transferred to an initial polycondensationreaction tank. After completion of transfer, the initialpolycondensation reaction tank was heated to gradually raise thetemperature to 205° C. Thereafter, the pressure was gradually reduced,followed by a reaction at 130 Pa to perform a reaction of increasing themolecular weight of aliphatic polycarbonate diol. After two hours, thecontent was transferred to a later polycondensation reaction tank. Themolecular weight of aliphatic polycarbonate at transfer was 20000. Intothe later polycondensation reaction tank was charged 236.4 parts by massof chips of polybutylene terephthalate (PBT) having the number averagemolecular weight of 30000 and the moisture amount of 80 ppm, 0.34 partsby mass of trimethylol propane was added, and the temperature wasgradually raised to 245° C. while stirring. The pressure in the can wasretained at 130 Pa and, after the internal temperature reached 245° C.,it was confirmed that the resin became transparent in 1 hour, and theblocking reaction was completed. The content was removed, and cooled toobtain a polyester-polycarbonate type thermoplastic polyester elastomer.Each physical property of the resulting polyester-polycarbonate typethermoplastic polyester elastomer was measured, and results are shown inTable 2. The polyester-polycarbonate type thermoplastic polyesterelastomer obtained in the present Example had all good properties, andwas of high quality.

Comparative Example 1

Without performing reactions in the esterification reaction tank and theinitial polycondensation reaction tank in the method of Example 1, 100parts by mass of polybutylene terephthalate (PBT) having the numberaverage molecular weight of 30000 and 43 parts by mass of polycarbonatediol (polycarbonate diol UH-CARB200, manufactured by Ube Industries,Ltd.) were charged into the later polycondensation reaction tank, andthe temperature was gradually raised to 245° C. while stirring. Thepressure in the can was retained at 130 Pa and, after the internaltemperature reached 245° C., it was confirmed that the resin becametransparent in 10 minutes, and the content was removed, and cooled toobtain a polyester-polycarbonate type thermoplastic polyester elastomer.Results are shown in Table 2. The polyester-polycarbonate typethermoplastic polyester elastomer obtained in the present ComparativeExample was inferior in blocking property and blocking propertyretainability. Further, the elastomer had the low reduced viscosity, andwas inferior in heat aging resistance, and was of low quality. Inaddition, since the molecular weight was low, a flexural modulus couldnot be measured.

Comparative Example 2

Without performing reactions in the esterification reaction tank and theinitial polycondensation reaction tank in the method of Example 4, 100parts by mass of polybutylene terephthalate (PBT) having the numberaverage molecular weight of 30000, and 43 parts by mass of aliphaticcopolymerized polycarbonate diol (polycarbonate diol T5652, manufacturedby Asahi Kasei Chemicals Corporation, molecular weight 2000, copolymerof 1,6-hexanediol and caprolactone, amorphous) were charged into areaction can in the later polycondensation reaction tank, and thetemperature was gradually raised to 245° C. while stirring. The pressurein the can was retained at 130 Pa and, after the internal temperaturereached 245° C., it was confirmed that the resin became transparent in10 minutes, and the content was removed, and cooled to obtain apolyester-polycarbonate type thermoplastic polyester elastomer. Resultsare shown in Table 2.

The polyester-polycarbonate type thermoplastic polyester elastomerobtained in the present Comparative Example was inferior in blockingproperty and blocking property retainability, and was of low quality ascompared with the polyester-polycarbonate type thermoplastic polyesterelastomer obtained in Example 4. In addition, since the molecular weightwas low, a flexural modulus could not be measured.

Example 11

According to the method of Example 1, at transfer of the product of thereaction of increasing the molecular weight of aliphatic polycarbonatediol to the later polycondensation reaction tank, PBT used in Example 1was simultaneously charged through another supply port in the moltenstate using a biaxial extruder and, according to the same manner as thatof Example 1, a polyester-polycarbonate type thermoplastic polyesterelastomer of Example 11 was obtained. Results are shown in Table 3.

The polyester-polycarbonate type thermoplastic polyester elastomerobtained in the present Example had equivalent quality to that of thepolyester-polycarbonate type thermoplastic polyester elastomer obtainedin Example 1, and was of high quality.

Example 12

In the method of Example 1, 236.4 parts by mass of the PBT chips used inExample 1 were charged into the later polycondensation reaction tank inadvance, they were melted at 245° C. and the pressure in the can of 130Pa, and was returned to the normal pressure with nitrogen prior totransfer. According to the same manner as that of Example 1 except thataliphatic polycarbonate having the molecular weight which had beenincreased by the same method as that of Example 1 was transferred to thelater polycondensation reaction tank and, after completion of thetransfer, the blocking reaction was performed, a polyester-polycarbonatetype thermoplastic polyester elastomer of Example 12 was obtained.Results are shown in Table 3.

The polyester-polycarbonate type thermoplastic polyester elastomerobtained in the present Example had equivalent quality to that of thepolyester-polycarbonate type thermoplastic polyester elastomer obtainedin Example 1, and was of high quality.

Example 13

According to the same manner as that of Example 11 except that the samepolyester production apparatus as the general-use polyester productionapparatus used in Example 1 was provided, and PBT produced in the oneproduction apparatus was charged in the molten state in the method ofExample 1, a polyester-polycarbonate type thermoplastic polyesterelastomer of Example 13 was obtained. Results are shown in Table 3.

The polyester-polycarbonate type thermoplastic polyester elastomerobtained in the present Example had equivalent quality to that of thepolyester-polycarbonate type thermoplastic polyester elastomer obtainedin Example 11, and was of high quality.

Example 14

According to the same manner as that of Example 1 except that aprocedure of mixing aliphatic polycarbonate diol and diphenyl carbonatein the esterification reaction tank was omitted, aliphatic polycarbonatediol and diphenyl carbonate were charged into the initialpolycondensation reaction tank, and a reaction of increasing themolecular weight of aliphatic polycarbonate diol was initiated, apolyester-polycarbonate type thermoplastic polyester elastomer ofExample 14 was obtained. Results are shown in Table 3.

The polyester-polycarbonate type thermoplastic polyester elastomerobtained in the present Example had equivalent quality to that of thepolyester-polycarbonate type thermoplastic polyester elastomer obtainedin Example 1, and was of high quality.

Example 15

According to the same manner as that of Example 6 except that using thegeneral-use polyester production apparatus consisting of each one of theesterification reaction tank and the polycondensation reaction tank,aliphatic polycarbonate diol and 4,4′-diphenylmethane diisocyanate weresupplied to the esterification reaction tank through separate supplyports, and a reaction of increasing the molecular weight of aliphaticpolycarbonate diol was performed in the esterification reaction tank,and the blocking reaction was performed in the polycondensation reactiontank, a polyester-polycarbonate type thermoplastic polyester elastomerof Example 15 was obtained. Results are shown in Table 3.

The polyester-polycarbonate type thermoplastic polyester elastomerobtained in the present Example had equivalent quality to that of thepolyester-polycarbonate type thermoplastic polyester elastomer obtainedin Example 6, and was of high quality.

Example 16

According to the method of Example 1, the product of the reaction ofincreasing the molecular weight of aliphatic polycarbonate diol wastransferred to a storage tank, and was stored at 150° C. under thenitrogen atmosphere. A few batches were stored. Thereafter, according tothe same manner as that of Example 1 except that 101.3 parts by mass ofthe molecular weight increasing reaction product was transferred to thelater polycondensation reaction tank using a metering pump, apolyester-polycarbonate type thermoplastic polyester elastomer ofExample 16 was obtained. Results are shown in Table 3.

The polyester-polycarbonate type thermoplastic polyester elastomerobtained in the present Example had equivalent quality to that of thepolyester-polycarbonate type thermoplastic polyester elastomer obtainedin Example 1, and was of high quality.

Example 17

Into an esterification reaction tank of a general-use polyesterproduction apparatus consisting of one esterification reaction tank andtwo polycondensation reaction tanks were charged 100 parts by mass ofaliphatic polycarbonate diol (carbonate diol UH-CARB200, manufactured byUbe Industries, Ltd., molecular weight 2000, 1,6-hexanediol type) and8.6 parts by mass of diphenyl carbonate, and materials werehomogeneously mixed and transferred to an initial polycondensationreaction tank. After completion of transfer, the temperature of theinitial polycondensation reaction tank was heated to gradually raise thetemperature to 205° C. Thereafter, the pressure was gradually reduced,followed by a reaction at 130 Pa to perform a reaction of increasing themolecular weight of aliphatic polycarbonate diol. After two hours, thecontent was transferred to a later polycondensation reaction tank. Amolecular weight of aliphatic polycarbonate diol at transfer was 10000.Into the later polycondensation reaction tank was charged 236.4 parts bymass of polybutylene terephthalate (PBT) chips having the number averagemolecular weight of 30000, and the moisture amount of 80 ppm, and thetemperature was gradually raised to 240° C. while stirring. The pressurein the can was retained at 130 Pa and, after the internal temperaturereached 240° C., it was confirmed that the resin became transparent inone hour to complete a blocking reaction, 1.01 parts by mass oftrimellitic anhydride was added, followed by stirring at the normalpressure for 15 minutes to complete the reaction. The content wasremoved, and cooled to obtain a polyester-polycarbonate typethermoplastic polyester elastomer. Each physical property of theresulting polyester-polycarbonate type thermoplastic polyester elastomerwas measured. Results are shown in Table 4. The polyester-polycarbonatetype thermoplastic polyester elastomer obtained in the present Examplehad all good properties, and was of high quality.

Example 18

Into an esterification reaction tank of a general-use polyesterproduction apparatus consisting of one esterification reaction tank andtwo polycondensation reaction tanks were charged 100 parts by mass ofaliphatic polycarbonate diol (carbonate diol UH-CARB200, manufactured byUbe Industries, Ltd., molecular weight 2000, 1,6-hexanediol type) and10.0 parts by mass of diphenyl carbonate, and materials werehomogeneously mixed, and transferred to an initial polycondensationreaction tank. After completion of transfer, the initialpolycondensation reaction tank was heated to gradually raise thetemperature to 205° C. Thereafter, the pressure was gradually reduced,followed by a reaction at 130 Pa to perform a reaction of increasing themolecular weight of aliphatic polycarbonate diol. After two hours, thecontent was transferred to a later polycondensation reaction tank. Themolecular weight of aliphatic polycarbonate at transfer was 30000. Intothe later polycondensation reaction tank was charged 101.3 parts by massof chips of polybutylene terephthalate (PBT) having the number averagemolecular weight of 30000 and the moisture amount of 80 ppm, 0.32 partsby mass of trimethylolpropane was added, and the temperature wasgradually raised to 240° C. while stirring. The pressure in the can wasretained at 130 Pa and, after the internal temperature reached 240° C.,it was confirmed that the resin became transparent in one hour, theblocking reaction was completed, 1.23 parts by mass of trimelliticanhydride was added, and the mixture was stirred at the normaltemperature for 15 minutes, and the reaction was completed. The contentwas removed, and cooled to obtain a polyester-polycarbonate typethermoplastic polyester elastomer. Each physical property of theresulting polyester-polycarbonate type thermoplastic polyester elastomerwas measured. Results are shown in Table 4. The polyester-polycarbonatetype thermoplastic polyester elastomer obtained in the present Examplehad all good properties, and was of high quality.

Example 19

Into an esterification reaction tank of a general-use polyesterproduction apparatus consisting of one esterification reaction tank andtwo polycondensation reaction tanks were charged 100 parts by mass ofaliphatic polycarbonate diol (carbonate diol UH-CARB200, manufactured byUbe Industries, Ltd., molecular weight 2000, 1,6-hexanediol type), and10.0 parts by mass of diphenyl carbonate, and materials werehomogeneously mixed, and transferred to an initial polycondensationreaction tank. After completion of transfer, the initialpolycondensation reaction tank was heated to gradually raise thetemperature to 205° C. Thereafter, the pressure was gradually reduced,followed by a reaction at 130 Pa to perform a reaction of increasing themolecular weight of aliphatic polycarbonate diol. After two hours, thecontent was transferred to a later polycondensation reaction tank. Themolecular weight of aliphatic polycarbonate at transfer was 30000. Intothe later polycondensation reaction tank was charged 101.3 parts by massof chips of polybutylene terephthalate (PBT) having the number averagemolecular weight of 30000 and the moisture amount of 80 ppm, and thetemperature was gradually raised to 240° C. while stirring. The pressurein the can was retained at 130 Pa and, after the internal temperaturereached 240° C., it was confirmed that the resin became transparent inone hour, the blocking reaction was completed, 0.95 parts by mass ofRikacid TMEG-200 (manufactured by New Japan Chemical Co., Ltd.) wasadded, the mixture was stirred at the normal pressure for 15 minutes,and the reaction was completed. The content was removed, and cooled toobtain a polyester-polycarbonate type thermoplastic polyester elastomer.Each physical property of the resulting polyester-polycarbonate typethermoplastic polyester elastomer was measured, and results are shown inTable 4. The polyester-polycarbonate type thermoplastic polyesterelastomer obtained in the present Example had all good properties, andwas of high quality.

TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Reduced Viscosity(dl/g) 1.20 1.15 1.19 1.15 1.20 1.15 1.09 Melting Point (° C.) 213 218216 213 224 208 211 Average Chain Length of 11 15 13 12 8 9 10 HardSegment (n) Average Chain Length of 8 9 9 8 5 6 7 Soft Segment (m)Blocking Property (B) 0.22 0.18 0.19 0.21 0.33 0.28 0.24 Block Property⊚ ⊚ ⊚ ⊚ ◯ ⊚ ⊚ Retainability Tensile Strength at Break 32.0 33.0 32.031.0 34.2 30.0 31.0 (MPa) Flexural Modulus (MPa) 230 220 230 210 240 210220 Heat-Aging Resistance 60 60 60 55 50 50 50 (Retention Rate: %)Water-Aging Resistance 97 95 98 95 95 90 95 (Retention Rate: %)

TABLE 2 Comp. Comp. Ex. 8 Ex. 9 Ex. 10 Ex. 1 Ex. 2 Reduced 1.20 1.251.23 0.50 0.52 Viscosity (dl/g) Melting Point (° C.) 206 202 212 190 190Average Chain Length 8 5 11 4 4 of Hard Segment (n) Average Chain Length6 4 8 2 2 of Soft Segment (m) Blocking Property (B) 0.29 0.45 0.22 0.750.75 Block Property ⊚ ◯ ⊚ X X Retainability Tensile Strength at 29.528.2 31.0 5 5 Break (MPa) Flexural Modulus 106 75 220 — — (MPa)Heat-Aging Resistance 63 64 91 0 0 (Retention Rate: %) Water-Aging 95 9696 75 70 Resistance (Retention Rate: %)

TABLE 3 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16 Reduced Viscosity(dl/g) 1.19 1.22 1.18 1.20 1.15 1.20 Melting Point (° C.) 214 215 214211 209 215 Average Chain Length of 12 13 12 10 9 13 Hard Segment (n)Average Chain Length of 8 9 8 7 6 9 Soft Segment (m) Blocking Property(B) 0.21 0.19 0.21 0.24 0.28 0.19 Block Property ⊚ ⊚ ⊚ ⊚ ⊚ ⊚Retainability Tensile Strength at Break (MPa) 32.5 34.0 32.0 32.2 30.033.0 Flexural Modulus (MPa) 230 230 220 230 210 220 Heat-AgingResistance 60 60 60 55 50 65 (Retention Rate: %) Water-Aging Resistance98 97 96 95 90 98 (Retention Rate: %)

TABLE 4 Ex. 17 Ex. 18 Ex. 19 Reduced 1.15 1.30 1.32 Viscosity(dl/g)Melting Point(° C.) 215 208 209 Average Chain Length 13 6 7 of HardSegment (n) Average Chain Length 9 7 10 of Soft Segment (m) BlockingProperty (B) 0.19 0.31 0.24 Block Property ⊚ ⊚ ⊚ Retainability TensileStrength at 33.0 27.5 28.5 Break (MPa) Flexural Modulus 220 80 80 (MPa)Heat-Aging Resistance 60 67 66 (Retention Rate: %) Water-Aging 93 97 98Resistance (Retention Rate: %)

The polyester-polycarbonate type thermoplastic polyester elastomeraccording to the present invention has been explained above based on aplurality of Examples, but the present invention is not limited to thefeatures described in the above Examples and the features may beappropriately modified by appropriately combining features described inrespective Examples in the range that the gist is not departed.

INDUSTRIAL APPLICABILITY

The process for producing a polyester-polycarbonate type thermoplasticpolyester elastomer of the present invention has an advantage that, byintroducing a step (step 1) of increasing the molecular weight ofaliphatic polycarbonate diol by a reaction of an aliphatic polycarbonatediol and a chain extender prior to a step (step 2) of reacting aliphaticpolycarbonate diol and an aromatic polyester in the molten state whichhas been previously known, a polyester-polycarbonate type thermoplasticpolyester elastomer of high quality having the following properties canbe economically and stably produced by a simple method of increasing themolecular weight of aliphatic polycarbonate to be supplied to a blockingreaction. In addition, in the process, the step 1 and the step 2 arepreferably performed in separate reaction tanks, and the process has anadvantage that the elastomer can be produced utilizing a general-usepolyester production apparatus using a system in which atransesterification or esterification reaction and a polycondensationreaction are preformed in separate reaction tanks.

In addition, the polyester-polycarbonate type thermoplastic polyesterelastomer of the present invention obtained by the process has improvedblocking property and blocking retainability while characteristic of thepolyester-polycarbonate type thermoplastic polyester elastomer beinggood in heat resistance, and excellent in heat aging resistance, waterresistance and low temperature property are maintained. Due to highblocking property, reduction in heat resistance resulting from reductionin the melting point is suppressed, and a mechanical nature such as ahardness, a tensile strength, and a modulus is improved. In addition,since due to improvement in blocking property retainability, fluctuationin blocking property is suppressed at molding processing, uniformity ofquality of molded articles can be enhanced. In addition, the propertiescan enhance recycle property, leading to reduction in environmental loadand the cost. Therefore, since the polyester-polycarbonate typethermoplastic polyester elastomer of the present invention has theaforementioned excellent properties and advantages like this, it can beused in various molding materials including fibers, films, and sheets.In addition, it is also suitable in elastic yarns, and molding materialssuch as boots, gears, tubes, and packings and, for example, is useful inutility of automobiles and household appliances requiring heat agingresistance, water resistance and low temperature property, specifically,utility such as joint boots, and electric wire covering materials.Particularly, the elastomer is suitably used as materials for partsrequiring high heat resistance such as joint boots used at a peripheryof automobile engines and electric covering materials. Therefore, thepresent invention greatly contributes to the industrial area.

1. A process for producing a polyester-polycarbonate type thermoplasticpolyester elastomer in which a hard segment consisting of a polyesterconstructed of aromatic dicarboxylic acid, and an aliphatic or alicyclicdiol, and a soft segment consisting mainly of aliphatic polycarbonateare connected, comprising at least the following steps: Step 1: a stepof obtaining the aliphatic polycarbonate with the increased molecularweight by a reaction of aliphatic polycarbonate diol and a chainextender, Step 2: a step of reacting the aliphatic polycarbonate and thepolyester in the molten state, wherein the number average molecularweight of the aliphatic polycarbonate is 7000 to
 70000. 2. The processfor producing the polyester-polycarbonate type thermoplastic polyesterelastomer according to claim 1, wherein the step 1 and the step 2 areperformed in different reaction tanks.
 3. A polyester-polycarbonate typethermoplastic polyester elastomer obtained by the process as defined inany one of claim 1 or 2, characterized in that when a cycle of raisingthe temperature of a polyester-polycarbonate type thermoplasticpolyester elastomer from room temperature to 300° C. at the temperatureraising rate of 20° C./min using a differential scanning calorimeter,retaining the temperature at 300° C. for 3 minutes, and lowering thetemperature to room temperature at the temperature lowering rate of 100°C./min is repeated three times, the melting point difference (Tm1-Tm3)between the melting point (Tm1) obtained by first measurement and themelting point (Tm3) obtained by third measurement is 0 to 50° C.
 4. Thepolyester-polycarbonate type thermoplastic polyester elastomer accordingto claim 3, wherein the hard segment consists of a polybutyleneterephthalate unit, and the melting point of the resultingpolyester-polycarbonate type thermoplastic polyester elastomer is 200 to225° C.
 5. The polyester-polycarbonate type thermoplastic polyesterelastomer according to claim 3, wherein the hard segment consists of apolybutylene naphthalene unit, and the melting point of the resultingpolyester-polycarbonate type thermoplastic polyester elastomer is 215 to240° C.
 6. The polyester-polycarbonate type thermoplastic polyesterelastomer according to claim 3, wherein letting the average chain lengthof the hard segment to be x, and letting the average chain length of thesoft segment to be y, calculated using nuclear magnetic resonance (NMRmethod), the average chain length (x) of the hard segment is 5 to 20,and blocking property B calculated by the following equation (1) is 0.11to 0.45,B=1/x+1/y  (1).
 7. The polyester-polycarbonate type thermoplasticpolyester elastomer according to claim 6, wherein the hard segmentconsists of a polybutylene terephthalate unit, and the melting point ofthe resulting polyester-polycarbonate type thermoplastic polyesterelastomer is 200 to 225° C.
 8. The polyester-polycarbonate typethermoplastic polyester elastomer according to claim 6, wherein the hardsegment consists of a polybutylene naphthalene unit, and the meltingpoint of the resulting polyester-polycarbonate type thermoplasticpolyester elastomer is 215 to 240° C.